Detergent sulphonic acid and sulphate salts of certain amphoteric detergents



United States Patent DETERGENT SULPHONIC ACID AND SUL- PHATE SALTS OF CERTAIN AMPHOTERIC DETERGENTS Hans S. Mannheimer, New York, N. Y.

No Drawing. Application May 24, 1956, Serial No. 586,921

Claims. (Cl. 260-401) This invention relates to novel compositions and to methods for making them. In one of its more spec fic aiigects, theinvention is directed to methods of making tam, to novel derivatives of a certain class of amino car- .boxylicacid metal salts, which I shall hereinafter refer to as ,amino acid metal salts.

in which R is a hydrocarbon radical of at least 6 carbon atoms and preferably 6-18 carbon atoms, and for most purposes R is preferably such a radical which may be either aliphatic and straight or branch chain or cycloaliphatic or aliphatic-aromatic, with the aliphatic portion being attached .to an aromatic nucleus and having at least 3 carbon atoms; Y and Y1 are each selected from the class consisting of Re and Rz-COOM; R2 is an organic group selected from the class consisting of (a) aliphatic, aromatic or aromatic-aliphatic hydrocarbon groups of 1-12 carbon atoms, such as CHz, -C2H4, -C3Hs-, -C4Hs, C5H1o, C6H10--, C6H4, CsH4CH2-, (b) hydroxy substituted aliphatic hydrocarbon groups of l-l2 carbon atoms, illustrative examples of which are CH2CHOHCH2-, CH2CHOHCHOHCH2-, (c) aliphatic ether groups, each of said groups having at least one ether oxygen linkage therein and otherwise being hydrocarbon of 2-12 carbon atoms, illustrative examples of which are (d) aliphatic ether groups, each of said group having at least one ether oxygen linkage therein and otherwise being hydroxy substituted hydrocarbon of 212 carbon atoms, illustrative example of which is R6 is selected from the class consisting of monovalent radicals otherwise defined in (a)(d), examples of which are --CH3, C2H5, C3H7, C4H9, C5H11, C6H11, -C6H5, CsH4CH3, -C2H4OH, -CH2CHOHCH2OH etc., C2H4OCH3, etc.; M is an alkali metal and preferably sodium or potassium; and A is selected from the class consisting of halogens and hydroxyl (OH) and Such amino acid metal salts may be prepared in a number of different ways Well known to the art:

For example, 1 mole of R-NH2 may be reacted with one mole of RsCl and with the use of caustic soda produced HCl is removed to provide which, in turn, is reacted with an equimolecular proportion of R801 and the produced HCl is removed to provide One mole of is reacted with one mole of an alkali metal salt of monochlormonocarboxylic acid either in aqueous or alcohol medium to provide a starting material:

If desired the C1 of such starting materials may be substituted by OH to provide equivalent starting materials by reacting it with an alkali metal hydroxide MOH, whereby Cl is substituted by OH and MCI is formed.

Or, 1 mole of RNH2 may be reacted with 1 mole of a monohalomonocarboxylic acid together with 2 moles of caustic soda to provide Rz-CO OM which in turn may be reacted with an equimolecular proportion of a monohalomonocarboxylic acid together with a dimolecular proportion of caustic soda to provide:

which may also be produced 'by reacting 1 mole of R-NHz with 2 mols of a monohalomonocarboxylic acid together with 4 moles of caustic soda. Then 1 mole of Rz-OOOM RN\ Ra-C 0 0M may be reacted with 1 mole of R601 to provide:

n R-N-Ri-C 0 0M 01 Rz-COOM which compound may have the Cl replaced by OH by reaction with MOI-I.

Or, 1 mole of may be reacted with 1 mole of monochlormonohalocarboxylic acid to provide:

which if desired may have its Cl replaced by OH by the use of caustic soda.

The monohalocarboxylic acids employed are preferably monochloracetic, monochlorpropionic, monochlorlactic, and the alkali employed is preferably NaOH or KOH.

The following Examples A-I and A-1 to 1-1 are given merely by way of illustrating in general methods which may be employed for producing examples of starting materials employed in the practice of this invention, such methods being known to the art and, as such, are no part of this invention.

Example A 1 mole of C12H25NH2 is reacted with 1 mole of methyl chloride and then reacted with NaOI-I to remove the HCl formed to provide and 1 mole proportion thereof is reacted with 1 mole of methyl chloride and then reacted with NaOH to provide CuHu-N and then 1 mole proportion thereof is reacted with 1 mole of sodium salt of monochloracetic acid to provide:

CHI

CuHzr-N-CH:

1 CHa-C ONE.

hereinafter known as product A and which may be reacted with an equimolecular proportion of NaOH to provide a compound the same as product A, except that the 01 thereof is replaced by OH and such compound is here inafter known as product A-1.

Example B 1 mole of hexyl benzyl amine:

CeHrr-N C r-Cs is reacted with 1 mole of monochlorlact-ic acid, together with 2 moles of sodium hydroxide to provide:

CHzCHOH-C O ONa CsHn-N CHr-CsHs then 1 mole thereof is reacted with one mole of sodium salt of monochloracetic acid to provide:

CHr-COONa CaH1sNGH:CHOHCOONa l CHz-CeHs hereinafter known as product B and which may be reacted with an equimolecular proportion of NaOH to replace Cl with OH and is hereinafter known as product B-l.

Example C 1 mole of lauryl phenyl amine:

CcHs

C1:HuN

then 1 mole thereof is reacted with 1 mole of sodium salt of monochloraceti'c acid toprovide:

CHz-COONa C12H25-N-CsH5 l O:|H40CHzCOONa hereinafter known as product C which may be treated with an equimolecular proportion of caustic soda to replace the Cl to OH to provide product C-l.

Example D Said compound is then reacted with an equimolecular proportion of sodium salt of monochloracetic acid to provide:

hereinafter known as product D which may be treated with equimolecular proportion of NaOH to replace Cl with OH and is hereinafter known as product D-1.'

Example E 1 mole of diethoxyamine is reacted with C12H25B1' and the HBr is reacted with NaOH. The resulting organic compound is reacted with 1 mole of monochlorpropionic acid, together with 2 moles of caustic soda or with acrylonitrile and subsequently hydrolized, to provide:

CzHrCOONa.

CnHrs-N (C2H40)2H and 1 mole thereof is reacted with 1 mole of sodium salt of monochloracetic acid to provide:

C2H4COONa CnHzr-N-C H2C O O Na Cl (C2H4O)2H hereinafter known as product E which may be reacted with equimolecular proportion of NaOH to replace Cl with OH to provide product E-l.

Examples F and G 1 mole of C12H25-NH2 is reacted in the presence of 2 moles of NaOH with the following respective compounds:

ClC6H4COOH and ClCH2CsH4COOH to provide the respective compounds which may be respectively reacted with equimolecular proportion of monochloracetic acid in the presence of dimolecular proportion of NaOH, and the resulting compounds subsequently reacted with equimolecu-lar proportion of sodium salt of monochlorpropionic acid to provide:

CsHr-COONa Cn r -OH:OOONe Cl CoHt-COONa hereinafter known as products F and G respectively, which may be reacted with equ-iiiiole'cular proportions of NaOH to replace Cl with OH- to provide compounds hereinafter known as products F-l and 6-1 respectively.

soda, and the resultant organic reaction product is reacted with an equimolccular proportion of sodium salt bf monochloracetic acid to provide:

CHzCHOHCHzOH C0Hi0'ITTCH2C0ONa c1 car-000m h i aiter known as product H which may be reacted ith equimolecular proportion of NaOH to replace Cl ifl fOH and provide product H1.

Example I k 1 mole of CsH19C6H4 2 is reacted with 2 moles ..ofjmonochloracetic acid, together with 4 moles of KOH lut'o' provide:

CHr-C 0 OK CoHw-CoH4-N CHz-QO or:

and 1 mole thereof is reacted with 1 mole of potassium salt monochlorpropionic acid to provide:

This compound, hereinafter known as product I, may be reacted with 1 mole KOH to replace the Cl thereof with OH to provide compound hereinafter known as product I-l.

The radical R of all of the formulas hereinbefore and hereinafter set forth is that hercinbefore defined in connection with Formula 1. Instead of employing monochloracetic acid, any other appropriate monohalomono-- carboxylic acid, such as monochlorpropionic, monochlorlactic acids, etc. may be employed. Thus, by merely substituting the particular monohalomonocarboxylic acid for those used in the production or" the particular compounds hereinbefore set forth, and/or by employing the various radicals and groups for R6 and R2 but within the definitions thereof as heretofore defined, a very great number of products X, examples of which are products A to I, and A-1 to 14, are amino acid metal salts, which may be employed as starting materials or reactants in the practice of this invention.

Prior to this invention, it was known that cationic surface active agents and anionic surface active agents when together in aqueous solution resulted in the production or formation of water-insoluble compounds; and that adding an anionic surface active agent to an aqueous solution of another anionic surface active agent resulted in a mere physical combination of said agents and that no reaction would occur between them.

Said amino acid metal salts" normally behave anionically in aqueous solutions having a pH above 7, and consequently it was expected that said amino acid metal salts when in aqueous solution together with anionic surface a en at th w u e ssmb ie alu qall 9 .11% and that no. chemical reaction. would there between. In. the. course. of my. expecimentationsl have discovered that said amino acid metal salts.- could be reacted with certain anionic surface active agents at a pH above 7 to produce water-soluble reaction products. Not only did I make said discovery, but I. further discovered that, water. solutions. of such reaction. products had viscosities greater-than corresponding aqueous solutions, of the. amine. acid metal. salts. and; also. exhibited better foaming characteristics than. did-.said. amino acid metal salts in very low dilutions under extreme water hardness conditions. Said reaction products are nontoxic and non-irritating to the human skin, They have been found eminently useful. as generalv utility detergents, such as for. car washing, dish washing, clothes. washing, etc. Said amino acid metal salts, as. well as. compounds of Formula II hereinafter described, and such amine. acid metal salts and compounds of-Eormula H in more physical mixtures, when used as. components. of shampoos cause stinging and sometimes slight irritation of the eyes when such shampoos were used and water. solutions thereof accidentally reached the eyes. I have further. discovered that the reaction. products of this invention caused practically. no irritation or. stinging of the. eyes when employed as components of shampoos.

According to this invention, one or a. combination of two ormore of said amino acid metal saltsof-the general structural Formula I are reacted with one or a com-. bination oftwo or more anionic, surface active agents. of the following. general'structural- Formula II- to provide novel, water-soluble compounds having the following general structural Formula III, andhaving high wetting,

detergcncy, and surface. active properties and capable of providing voluminous and stable foams in aqueous solutions, and which aqueous solutions are. substantially nonirritating to the skin and eyes of; normal human beings.

QRMU II o R: R( 3eI IR4'-XM FORMULA III 7 Y R-N Yl c l a nt-cooivr RCNRi-X wherein R3 is selected from the group consisting of (a) hydrogen, (b) aliphatic hydrocarbon radicals of 1-8 carbon atoms, (0) hydroxy substituted aliphatic hydro carbon radicals of l-8 carbon atoms, (d) aliphatic radicals, each of said radicals having at least one ether oxygen linkage therein and otherwise being hydrocarbon of 28 carbon atoms, (e) aliphatic radicals, each of said radicals having at least one ether oxygen linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-8 carbon atoms, (7) aliphatic radicals, each of said radicals having at least one carbonyl linkage therein and. otherwise being hydrocarbon of 28 carbon atoms, (g) aliphatic radicals, each of said radicals having at least one carbonyl linkage therein and otherwise being hydroxy substituted hydrocarbon of 28 carbon atoms; R4 is selected from the group consisting of (h) aliphatic, aroa matic, and aromatic aliphatic hydrocarbon" groups of 1-12 carbon atoms, (i) hydroxy substituted aliphatic, aromatic and aromatic-aliphatic hydrocarbon groups of 1-12 carbon atoms, aliphatic, aromatic and aromaticaliphatic groups having at least one other oxygen linkage therein and otherwise being hydrocarbon of 2'l2 carbon atoms, .(k) aliphatic, aromatic and aromatic-aliphatic groups, each of said groups having at least one other oxygen linkage therein and otherwise heinghydroxy'si bstituted hydrocarbon 'of 212 carlgonatqms; (I) aliphatic, aromatic and aromatic-aliphatic groups," each 'of 's'aid groups having a carbonyl linkage therein and otherwise I being hydrocarbon of 2-12 carbon atoms, (m) aliphatic, aromatic and aromatic-aliphatic groups, each of said groups having a carbonyl linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-12 carbon atoms, (n) aliphatic, aromatic and aromatic-aliphatic groups, each of said groups including a CONH- linkage therein and otherwise being hydrocarbon of 2-12 carbon atoms, aliphatic, aromatic and aromatic-aliphatic groups, each of said groups including a CONH- linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-12 carbon atoms; X is selected from the group consisting of S03, and 050s; and M is an alkali metal, preferably sodium or potassium; R, R2, Y, Y1 and M have been hereinbefore defined. 1

According to this invention, I react a compound of Formula I with a compound of Formula II to provide the novel and highly useful compounds of Formula III. In general this reaction is carried out in a solution containing compounds I and -II and to which a quantity of an acidic agent such as a strong mineral acid, as for example hydrochloric, sulphuric or its equivalent, has been added to lower the pH of the solution to a value of approximately 7 to approximately 9 and while maintaining the mass at a temperature between approximately 100- 200 F. In this reaction under the aforesaid conditions, the compounds of Formula III are produced, said compounds having high water solubility in spite of the fact that the number of carbon atoms in R is 6 or more. Such compounds of Formula III have an unexpected extremely high water-solubility, while the corresponding salt of cationic compounds are water-insoluble. The resulting aqueous solution can be used directly as a surface active agent, wetting agent or detergent for the purposes indicated for the amino acid metal sal While the quantities of the compound of Formula I and compound of Formula II may be equirnolecular for good yield of compounds of Formula III, I may employ an excess of either, and in general the mole ratio of a compound of Formula I to compound of Formula II may be 2 moles of the former to 1-3 moles of the latter.

One of the specific methods which I prefer to employ in carrying out an aspect of this invention is to first dissolve a compound of Formula I in water and then the pH thereof is adjusted to approximately 12-13 (measured electrically) by the addition of aqueous caustic soda if required so that when a compound of Formula II is added thereto, the pH of the solution of I and II will be at least 10 and generally 105-11. The temperature of said solution is raised to 100-200 F. and preferably in factory practice to approximately 140 F. Then a quantity of a compound of Formula II is dissolved in water in a separate container and this solution is added to said first solution and the mass is maintained in said temperature range while being constantly stirred, and an acidic agent is added thereto to reduce the pH thereof to a value below 10 and in the range of approximately 7 to 9, and preferably of approximately 8.2 to approximately 8.7. At the end of the acidic agent addition, the stirring is continued and the temperature of the mass maintained for about 10-20 minutes after which the solution is allowed to cool and is a finished product.

The following are specific examples merely given by way of illustrating the invention and are not to be taken by way of limitation, all parts being given by weight unless otherwise specified.

Example 1 An aqueous solution of 330 parts of product A in 570 parts of water is heated to approximately 140 F. and its pH (measured electrically) is adjusted by the addition of aqueous caustic soda to 12-13. While being constantly stirred and maintained at that temperature, there is added a solution of 400 parts of sodium salt of lauroylmonoethanolamide sglfae:

in 600 parts of water. Then while stirring and the temperature is maintained there is added thereto between about 30-40 parts of hydrochloric acid solution (32%) whereby the pH of the mass is lowered to a value in the range of 8.2 to 8.7. Stirring is continued and the temperature maintained for about 10 minutes more. The resultant product is a solution of the novel reaction prod-- uct having the following formula:

Employ the same procedure and components as set forth in Example 1, except that only about 200 parts of the sodium salt of lauroylmonoethanolamide sulfate are used. In this instance, the resultant product is a solution of the novel reaction product whose structural formula is shown in Example 1 together with unreacted prodnot A used, in the approximate proportion of two pant of the former to one of the latter. I

Employ the same procedure as that set forth in Exam l 1, but employ the components indicated in the followi Examples 3-29; the quantity of hydrochloric acid' I tion (32%) is variable to lower the pH to values i di cated in Example 1 to obtain the novel reaction products of said Examples 3-29.

Example 3 409 parts of product B in 615 parts of water. parts of lauroyltaurate sodium salt:

Ci1H;cCN-CzH4SOaNa in 600 parts of water. I

FORMULA OF NOVEL 410 parts of product C in 615 parts of water. parts of oleoyldiethanolamide sulfate sodium salt:

384 parts of product D in 576 par-ts of water. 400 parts of lauroyltriethoxyetheramide sulfate sodium salt:

in 600 parts of water.

FORMULA OF NOVEL REACTION PRODUCT CHr-COON8 CgHn-CeHr-N-CHr-C 0 ON?- 0 H CHLOE Par s of h yl uroy midodie h zyeths e ham n sulphate sodium salt:

03H) CQHlOH CnHe-O-N-QHQczm-o-sor-Na in .00 parts of water. t

FORMULA OF NOVEL REACTION PRODUCT 01111-0 O O Na C,;H N-CH;C 0 ONa 0 02 400111405 (CzHlOhH Example 7 .530 parts of product F in 195 par of water.

of lauroylamidoethylamidoacetylsulphate so Salli t 544 parts-lot product G in 816 parts of water. 300

parts of lauroyl sulfanilamide potassium salt:

CuHgr-( J-FIh-CsHA-SOr-K dissolved in 450 parts of water.

FORMULA OF NOVEL REACTION PRODUCT c [HA-C o 0 Na C nHas-NCHr-C O 0 Na.

GHaCo 4-C 0 ONa CflHW-dk-CtHkSOt Example 9 230parts of product H in 345 parts of water. 350 parts of lauroyl amido methyl methyl phenyl sulfonate sodium salt:

dissolved in 500 parts of water.

FORMULA OF NOVEL REACTION PRODUCT omonorrcmon Example -10 602 parts of product 1 in 903 parts of water. parts of lauroyl amido ethoxy methyl ethyl sulfate sodium salt:

GHQ-C 0 O K CoHrr-CoHr-N-CHr-C 0 OK 0 CsHAOCHl CaHr-COOK 400 dium 10 Exa ple 11 Employing the same procedure as that set forth in Example 1, except that product B is substituted for product A to provide another novel reaction product which is the same as that of Example 1, except that the structural formula of product B but lacking the halogen thereof is substituted for the corresponding part of prod not A therein.

Examples 12-14 Employing the same procedure as that set forth in Example 1, except that products D, E, and H are respectively substituted for product A to provide novel reaction products, which are respectively the same as that of Example 1 except that respective structural formulas of products D, E and H but lacking the halogens thereof are substituted for the corresponding part of product A therein.

Examples 15 and 16 Employing the same procedure as that set forth in Example 1, except that products C and F respectively are substituted for product A to provide novel reaction products which are respectively the same as that of Example 1, except that respective structural formulas of products C and F but lacking the halogens thereof are substituted for the corresponding part of product A therein.

Examples 17-29 -cnoncnoncmon,

-C zH4OCH3, C2H4OC2H2OH, -,-CH2CHOHOC2H5, --'CH2COCH3, -C2H4COC2H4OH, .CH2OHCOC2H5; whereby there are produced a number of other novel reaction products whose formulas are the same as the formula of the novel reaction product whose formula is within the definition of Formula 111 and shown in Example 3, except that the aforesaid respective radicals replace the H of the NH connected directly to the CO thereof.

Following the same procedure as that set forth in Example 1 and employing 1 mole of any of said other starting materials of Formula I respectively, and 1 mole of any of the other specific compounds of Formula 1-1 employed in Examples 1-29, a great number of other novel reaction products whose formulas are that of Formula III may be produced; and in addition, the specific reactants employed may differ from those employed herein, in varying R, R1, R2, and R3 within the definitions thereof, to provide a great number of other compounds of Formula III.

It is to be understood that instead of first adjusting the pH of the compound of Formula I to 12-13 before the addition of the-compound of Formula II, any other method may employed to obtain the condition whereby the pH of the solution of I and H is at least 10 and preferably 10.5-11 before the addition of the acidic agent to lower the pH of the mass to approximately 7 to approxi' mately 9. For example, I and Il may be dissolved together and this solution may, by the addition of caustic soda when required, have its pH adjusted to at least 10, and then at 200 F. is ready for the addition of the acidic agent to lower its pH to approximately 7 to approximately 9. If desired, the required amount of acidic agent may be added either before or after the solution of pH of at least 10 is brought to a temperature in the range of JO-200 F.

It is to be understood that when either $03 or 0803 is used in the specification and claims, it is meant to indicate either one or the other because of their obvious equivalency; it is also to be understood that the use of Na in the specification and claims is meant to indicate any of the other alkali metals because of their obvious equivalency; and it is also to be understood that the -CONH linkage when part of R4 in the specification and claims is meant to indicate it or -NI-ICO because of their obvious equivalency.

Since certain changes in carrying out the aforesaid processes and certain modifications in the compositions which embody the invention may be made without departing from its scope, it is intended that all matter contained in the description shall be interpreted as illustrative and not in a limiting sense.

It is also to be understood that the following claims are intended to cover all the generic and specific features of the invention herein described, and all statements of the scope of the invention which as a matter of language might be said to fall therebetween.

This application is a continuation-in-part of my co-pending application Ser. No. 575,300, filed April 2, 1956.

I claim:

l. A compound of the following formula:

in which R is a hydrocarbon radical selected from the group consisting of aliphatic hydrocarbon radicals of 6-18 carbon atoms, aliphatic-aromatic hydrocarbon radicals of 6-18 carbon atoms, with the aliphatic portion thereof having at least 3 carbon atoms; Y and Y1 are each selected from the class consisting of R6 and R2 is selected from the class consisting of (a) aliphatic and hydroxy substituted aliphatic hydrocarbon groups of 1-12 carbon atoms, (b) aliphatic ether groups, each of said groups having at least one oxygen linkage and otherwise being hydrocarbons of 2-12 carbon atoms, (a) aliphatic ether groups, each of said groups having at least one oxygen linkage and otherwise being hydroxy substituted hydrocarbons of 2-12 carbon atoms, (:1) aromatic and aliphatic-aromatic hydrocarbon groups having a maximum of 12 carbon atoms; Rs selected from the class consisting of monovalent radicals otherwise defined in (a)-(d); R3 is selected from the group consisting of ((1-1) hydrogen, (b-l) aliphatic hydrocarbon radicals of l-8 carbon atoms, (c-l) hydroxy substituted aliphatic hydrocarbon radicals of 1-8 carbon atoms, (d-l) aliphatic radicals, each of said radicals having at least one ether oxygen linkage therein and otherwise being hydrocarbon of 2-8 carbon atoms, (e-l) aliphatic radicals, each of said radicals having at least one ether oxygen linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-8 carbon atoms, (f-l) aliphatic radicals, each of said radicals having at least one carbonyl linkage therein and otherwise being hydrocarbon of 2-8 carbon atoms, (g-l) aliphatic radicals, each of said radicals having at least one carbonyl linkage therein and otherwise .12 being hydroxy substituted hydrocarbon of 2-8 carbon atoms; R4 is selected from the group consisting'of (h-l) aliphatic, aromatic, and aromatic-aliphatic hydrocarbon groups of 1-12 carbon atoms, (i-l) hydroxy substituted aliphatic, aromatic and aromatic-aliphatic hydrocarbon groups of 1-12 carbon atoms, (j-l) aliphatic, aromatic and aromatic-aliphatic groups having at least one ether oxygen linkage therein and otherwise being hydrocarbon of 2-12 carbon atoms, (k-l) aliphatic, aromatic and aromatic-aliphatic groups, each of said groups having at least one ether oxygen linkage therein and otherwise being hydroxy substituted hydrocarbon of 12-12 carbon atoms, (l-l) aliphatic, aromatic and aromatic-aliphatic groups, each of said groups having a carbonyl linkage therein and otherwise being hydrocarbon of 2-12 carbon atoms, (m-l) aliphatic, aromatic and aromatiealiphatic groups, each of said groups having a carbonyl linkage n CHr-COONa 0 R-ii-fiI-Cflit-O-SO:

in which R is hydrocarbon radical of 6-l8'carbon atoms.

3. A compound of the following formula:

CHz-C 00K a-N-orn-oo 0K 0 CzHtOCH; CzHt-C 0 OK in which R is hydrocarbon radical of 6-18 carbon atoms.

4. A compound of the following formula:

R-N-CH;

0 canon CHr-OOONa R-C-N-CzILO-SO: in which R is hydrocarbon radical of 6-18 carbon atoms.

5. A compound of the following formula:

CHa-COONa RNCH2COONa O H CEHlOH R- I I(CzH4O) SO3 in which R is hydrocarbon radical of 6-18 carbon atoms.

References Cited in the file of this patent UNITED STATES PATENTS Schoeller et a1. Dec. 28, 1937 Isbell Nov. 25, 1952 

1. A COMPOUND OF THE FOLLOWING FORMULA: 